Method of dehydrating a hydroxtl



Patented June 24, 1941 I METHOD OF DEHYDRATING A HYDROXYL- ATED FAT B FATTY ACID 0F THE RICINOLEIC SERIES Y Richard '1. Ubben, Elmhurst, and James R. Price,

In, Chicago, 111., assignors to Armstro &: Varnish Works, of Illinois No Drawing. Application October Serial No. 297,134

11: Paint Chicago, 111., a corporation 4 Claiins. (Cl. 260-393) This invention relates to a method of dehydrating a hydroxylated fat or fatty acid of, the ricinoleic series. More particularly this invention relates to the preparation of a dehydrated castor oil having drying properties and useful in the manufacture of protective films and coatings.

It has long been known to use drying oils, such as linseed, tung and the like in making protective coatings. These oils have also been used in the manufacture of modified alkyd resins, formed by the reaction of polybasic acids with polyhydric alcohols. All of these commonly used drying oils,

however, are unsaturated, and therefore oxygen absorptive by nature and are ready for use after a simple. refining operation.

More recently it has been proposed to convert particular non-drying oils, such as castor oil, into oils having drying properties. castor oil, its conversion into anunsaturated oil has been accomplished by means of dehydration, the removal of one molecule of water from each fatty acid radical contained in the castor oil resulting probably intwo double bonds in con- ;lugated position. The unsaturated oil so formed has drying properties renderinglt useful as a component of protective films and coatings, but such an oil has thus far not proved entirely sat lslactory because of possession of a slight residual tackiness that necessitates abnormal proportlons cl driers or of. hard resins to overcome. In

addition, methods of preparing this unsaturated oil from castor oil have proved cumbersome and costly, resulting in a definite increase in on over that or raw castor oil.

according to our present invention, castor oil. or other hydroxylated fat or fatty acid of the rlclholelc series, is converted into a dehydrated product having drying properties by reaction at a relatively high temperature with phthalic anhydrlde or phthalic acid. While it has previously been lznown that castor oil and 'phthalic anhy drlole, ll heated together at about 150 to 180 C... would term a relatively viscous oil, it was not heretofore appreciated, to the best of our knowledge, that a substantially completely dehydrated In the case of castor oil having good drying properties could be prepared fromcastor oil and phthalic anhydrlde by the use of notably higher temperatures, such as from 525 to 575 F.

We have found that if temperatures of that order of magnitude are employed, and preferably temperatures within the narrower range of M0 to 550 F., a clear, homogeneous dehydrated castor oil having good drying properties, and therefore useful in making protective films and coatings, can be produced. It has been known that a drying oil could be obtained by heating castor oil and phthalic anhydride. However, it is only after numerous experiments that we have determined that at about 545 F. a substantially completely dehydrated castor oil can be produced which is far superior in drying properties to a product preparedat higher or lower temperatures. At temperatures below 540 F. some dehydration takes place it is true, accompanied however with the formation of a large amount of ester polymers. At 525 F. for example, an oil which is only partially dehydrated is produced and which is very slow drying.- At 575 F. dehydration takes place with case, but as rapidly as it dehydrates it polymerizes to form large molecules which tend to block the remaining unclehydrated oil from the phthalic anhydride.

It is therefore an important object of this in vention to provide a method of dehydrating a hydroxylated lat or fatty acid of the ricinoleic series to obtain a product having valuable drying properties and useful as an ingredient in protective films and coatings.

it is a further important object of this invention to provide a relatively simple, economical process for preparing a dehydrated caster oil or @ther and further important objects of this invention will become apparent from the followin description and appended claims.

"the primary starting material for use in our method is a hydroxyiatedfat or fatty'acid, preferably oi the rlcinoleic series, the acids of which have the general lormula Cullen-:03. The acids of this series include ricinolelc acid, isoricinoleic cold, rlclnelaldie acid, ricinic acid and quince oil acid. instead oi the acids themselves, the glyc'er lde esters or such acids, that is, the corresponding tats, may be employed. In fact, our preferred starting material is castor oil itself, which contains a substantial proportion of ricinolein,

the simple triglyceride of ricinoleic acid.

One or the reasons for preferring to use castor oil as the starting material is its commercial availability. However, where caster oil is spccifh cally referred to in the examples given hereinafter, it will be understood that other members of the ricinoleic series of fats and fatty acids may be substituted in place thereof. In fact, ricinoleic acid itself constitutes an even more satisfactory starting material than the triglycerides, since it may be more easily converted into a resin product having outstanding drying properties. It is thus merely a question of cost and availability as to which member of the generic class is as a starting material.

In-practlcing our invention, using refined castor oil as the starting material, the eastor oil and a suitable proportion of phthalic anhydride or phthalic acid, are charged into a reaction vessel equipped with an outside source of heat, a mechanical agitator, a reflux condenser and an inlet for the introduction of a non oxidizirig gas, such as carbon dioxide. Reaction vessels of glass, enamel, nickel, iron, or any of the iron alloys such as Monel metal, stainless steel, or the like, may be satisfactorily employed. Non-calcining gases, or inert gases, other than carbon dioxide, such as nitrogen, flue gas, and the like, may be used to help to preserve the light color of the product.

The charge in the reaction vessel is gradually heated, with agitation, to a temperature of ice-- tween 525 and 575 F., preferably between 5&0 and 550 F., maintaining the charge at all times under a blanket of inert gas. During the progress of the reaction, water is split ofl from the castor oil as a. result of the esterification action 01' the phthalic anhydride. The temperature and other conditions maintained in the reflux con denser are such as to permit the escape or water vapor, while returning the reacting constituents to the sphere of reaction within the vessel. The length of time required to bring the reaction to substantial completion depends upon the temperature employed and upon the percentage of phthallc anhydride used. Temperatures higher or lower than the range specified cannot be setisfa-ctorlly used, because at lower temperatures the reaction proceeds too slowly to be economical, whereas at higher temperatures the danger of gelation is too great to make. such higher temperatures practical. The preferred temperature at which the reaction is carried out is 545 F or within the rangeoi from 546 to 550 R, within which range 01' temperatures thetime required for substantially complete reaction is from 5 to 7 hours. In general, if the temperature is maintained at between 525 and 575 F from 3 to 1 hours sufilces for the substantial completion of the reaction. While the reaction is preferably carried out at atmospheric pressures, reduced pressures may be employed.

The substantial completion of the reaction is' evidenced by the rapidity of drying of a thin film of the reaction product at elevated temperatures. By way of example, it a small proportion of cobalt naphthenate, say the equivalent oi. 0.5% of metallic cobalt by weight, or other suitable drier, is added to the reaction product, it should dry hard in from 1 to 2 hours if deposited as a thin film.

Since it is well known that secondary or beta hydroxyl groups are 'difi lcult to esteriiy and that, when-once esterified, the esters are very easily hydrolyzed or-broken down, it is believed that when castor oil is reacted upon by phthalic anhydride, the beta hydroxyl group of the fatty acid radical contained in castor oil is subject to assures weight of castor oil) has been used, the initial percentage of phthalic anhydride will crystallize out of a sample of the reaction mixture when the latter is cooled. In other words, although a great deal of water oi. esterification has been liberated, the phthalic anhydrlde, at this stage of the reaction, is still present in its free form.

After the reaction has progressed to a point where the castor oil is substantially completely dehydrated, however, phthalic anhydride will no longer crystallize out from the cooled reacted mass, provided that not more than 5% of phthalic anhydride by weight of the castor oil has initially been used.

It is thus evident that the mechanism of the reaction occurs in two stages involving:

(1) The union of a molecule of phthalic anhydride with the hydroxyl group of the fatty acid radical of castor oil to form an ester, releasing water, and

(2) The subsequent decomposition at higher temperatures oi this ester and the reformation of phthalic anhydride, resulting in a dehydrated castor oil with the unsaturated groups in conjugated positions.

In cases where less than 5% of phthalic anhydride by weight of the castor oil has been used after the completion of the reaction, there is no free phthalic anhydride which it is necessary subsequently to esteriiy. However, when larger percentages of phthalic anhydride are used to dehydrate the castor oil, it is advisable subsequently to esterify the free acidic group present with a polyhydric alcohol, thereby producing a modifled alkyd type resin of exceptional drying properties. The esterlfication of the free acidic groups with a polyh'yclric alcohol can-satisfactorilybe carried out at temperatures lower than those at which the primary reaction is effected, say at temperatures from 400 to 545 R, or, more preferably, at temperatures from 425 to 500 F.

The following examples will serve to illustrate preferred embodiments of our invention, but it will be understood that our invention is not to be limited to the specific examples:

Example 1 Parts by weight Refined castor oil 3900 Phthalic anhydride The castor oil and phthalic anhydride are placed in the reaction vessel and the temperature is gradually raised to about 545 F., where it is maintained for 6 hours. During thelater stages of the heating operation, the reflux condenser is entirely removed or the conditions of reflux so controlled as to permit the escape of water of dehydration from the sphere of the reaction. Upon cooling the reaction mass, 8. clear, homogeneousdehydrated castor oil is obtained. A thin iilm of this resinous product, upon the addition thereto of a fractional percentage of cobalt naphthenate, the equivalent, say. of 0.5% of metallic cobalt by weight, will dry in from 1 to 2 hours to give a hard, non-tacky coating.

While we have found that about 2%% of phthalic anhydride by weight of castor oil gives optimum results, where the acid groups remaining in the reaction mass are not to be subsequently esterified, it is feasible to vary this percentage between 1 and 5%. The presence of the free acid groups in the reaction product apparently accelerates drying.

' tion of the oil, while leaving a residue of mixed glycerides of dehydratedand unchanged castor oil fatty acids.

Example 2 Parts by weight Refinedcastor oil 3800 Phthalic anhydride v140 Glycerol 60 The castor oil and phthalic anhydride are placed in the reaction vessel and the temperature is gradually raised to about 545 F., where it is maintained for 6% hours. The product is then allowed to cool'to about 400 F., and the glycerol is added. The temperature is again gradually raised to about 450 F. and is maintained at that point until the free acidic groups have been esterified, as evidenced by a reduction in the acid value to about 5.0 or less.

The resulting resinous product resembles an a extremely heavy bodied oil, and may be used as such, or may be further modified by the incorporation of hard, oil-soluble resins to produce surface coating materials of widely variable properties, Upon the addition to this resinous product of a small amount of cobalt naphthenate, a thin film of the composition will dry hard in from 2 to 4 hours. There is a slight residual tack noticeable in films of this resin, even after the iilm is hard, but this is a characteristic of ex- With the foregoing proportions,advantage is taken of the extremely rapid dehydration oi castor oil that occurs when approximately equal weights of castor oil and phthalic anhydride are held within our preferred temperature range of from 540 to 550 F.

The phthalic anhydride "and castor oil are heated slowly to about 545 F. and held at that temperature for about 1 hour. evolution of water will practically have ceased.

. The fatty acids and glycerol are then added and the mixture heated for about 4 hours at about 450 F., at the end of which period the acid value of the reaction mass is from 10 to 12.

. Minutes Product of Example 1- Product of Example 2 14 Commercial product #1 Commercial product #2 20 Commercial product #3 62 tremely long-oil resins and may be eliminated bythe addition thereto of small amount of suitable varnish resins. v

- for 2 hours, at the end'of which period the product was found to have. an acid value of 5.6. The finished product isa very viscous oil or resinous material, which when thinned with mineral The resulting resinous product, when reduced with a suitable solvent, is ideal for enamels, where color retention, quick dry, and durability are important. As compared with other commercially available dehydrated castor oils, our resinous product possesses superior drying properties, as evidenced by the following table showing the time required for gelation at a temperature of 585 F.:

It will, of course, be understood that various detail of the process may be varied through a wide range without departing from the principles of this invention and it is, therefore, not the purpose to limit the patent granted hereon otherwise than necessitated by the scope oi'the appended claims.

We claim as our invention:

1. The method of dehydrating castor oil, which comprises heating to a temperature between 525 and 575 1?. a mixture consisting of castor oil and phthalic anhydride, the proportion of phthalic anhydride being insufllcient to esteriiy a substantial proportion of said castor oil but being capable by reaction'with successive correspond-.

ing increments of said castor oil of forming in- Example 3 Parts by weight Refined castor oil 3600 Phthalic anhydride 248 4 Glycerol 152 which within said temperature range is decomposed to release free phthalic anhydride for fur-' ther incremental reaction, and continuing the heating within said temperature range until substantially complete dehydration of said castor oil spirits, and driers added, gives a fast drying,

clear, hard film,

- Example 4 Parts by weight. Refined casto'r oil 1200 Phthalic anhydride 1184,, Linseed oil fatty acidsri Glycerol has been eflected to give directly dehydrated castor oil having conjugated double bonds.

2. The method of dehydrating a compound oi the group consisting of fats and fatty acids of the ricinoleic series, which comprises heating to between 525 and 575 -1". a mixture consisting essentially oi such compound of the riciuoleic series and a small proportion of a compound selected from the group consisting oi phthalic acid and phthalic anhydride, said proportion being lessthan sufiicient to substantially esterify said member, continuing heating to eiiect successively the iormation oismali amounts oi thephthalic ester of said member and the decomposition within said temperature range of said ester to reform free phthalic anhydride until substantially complete dehydration of said member has been eifected to give a product having conluzated double bonds.

3; The method of dehydrating castor oil, which At this point,

within that temperature range until by the suc cessively occurring reactions of forming small amounts of the uhthelic ester of castor oil and of decomposing said ester to release free phthalic army iizie c, substantially complete dehydration of se. d caster 011 within said temperature range has been effected to produce a dehydrated castor oil having conjugated double bonds.

A, fire method (if-dehydrating castor oil, which comprises heating to 9, temperature between 540 and 559 F, a reaction mixture consisting of cestor eii end gsirthelic enhydride, the propormcn of phtheiic enhyciride being insuficient to esterii'y heating within said temperature range until substeirtieily complete dehydration of said caster oi1- has been efiected to give directly dehydrated castor oil having conjugated double bonds.

' v" T. UBBEN. JAMES R. PRICE, JR. 

